WO2018041492A1 - Matières à mouler thermoplastiques - Google Patents

Matières à mouler thermoplastiques Download PDF

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Publication number
WO2018041492A1
WO2018041492A1 PCT/EP2017/069107 EP2017069107W WO2018041492A1 WO 2018041492 A1 WO2018041492 A1 WO 2018041492A1 EP 2017069107 W EP2017069107 W EP 2017069107W WO 2018041492 A1 WO2018041492 A1 WO 2018041492A1
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compositions
component
molding
mass
products according
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PCT/EP2017/069107
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German (de)
English (en)
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Jochen Endtner
Matthias Bienmüller
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Lanxess Deutschland Gmbh
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Priority to EP17752316.4A priority Critical patent/EP3507330B1/fr
Priority to CN201780053291.2A priority patent/CN109642071B/zh
Priority to JP2019511864A priority patent/JP6883093B2/ja
Priority to ES17752316T priority patent/ES2788711T3/es
Priority to KR1020197005668A priority patent/KR102341559B1/ko
Priority to US16/329,876 priority patent/US20190241736A1/en
Publication of WO2018041492A1 publication Critical patent/WO2018041492A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the invention relates to compositions and molding compositions to be produced therefrom and products based thereon in addition to polyethylene terephthalate at least one other polyester from the group of polyalkylene or polycycloalkylene, as well as at least one organic phosphinic salt and / or at least one organic Diphosphinklaresalz, and at least one condensed melamine derivative and at least a reaction product of a melamine derivative with phosphoric acids or condensed phosphoric acids.
  • variable thicknesses of the finished parts In order to take into account the variable thicknesses of the finished parts, this should be met in the same way both on test plates with at least 3mm wall thickness, as well as thin test plates with a maximum of 0.75mm wall thickness. In recent years, not least for ecological reasons increasingly halogen-free solutions are demanded.
  • EP 2 927 279 A1 describes compositions comprising PBT, phosphinic acid salts,> 4% by weight of a phosphazene compound and nitrogen-containing cyclic compounds which achieve a GWIT of at least 775 ° C. according to IEC60695-2-13 on plates of different thicknesses. There is also an indication that when using PBT + PET blends, the delay could be reduced, but with the restriction that the crystallization time is extended, which involved the disadvantage of extended cycle time, so that EP 2 927 279 A1 compositions with PBT as sole resin favored.
  • EP 1 945 708 B1 describes compositions comprising PBT, PET, a metal phosphinate melting below 310 ° C.
  • compositions and molding compositions or products based on blends of polyethylene terephthalate and at least one further polyalkylene terephthalate and / or polycycloalkylene terephthalate which are largely thermally stable against transesterification in the UL94 test with wall thicknesses> 0,75mm have a V-0 classification and show in the glow wire test according to IEC60695-2-13 even at a glow wire temperature of at least 800 ° C with wall thicknesses> 0.75mm no ignition.
  • No ignition in the glow wire test should be understood to mean that there is no flame, so the burning time of the flame is 0 seconds.
  • stable to transesterification means that the melting point of the highest-melting blend component, measured as an endothermic peak with the DSC method described in more detail below (differential scanning calorimetry [https://de.wikipedia.org/wiki/Dynamic_differential calorimetry]) during the second heating maximum 10 ° C below the melting point of the 1. Heating is located.
  • a DSC device of the Mettler DSC 822e type from Mettler Toledo, GNeillsee, Switzerland is charged with 10 ( ⁇ 2) mg of a compound to be tested and then heated under nitrogen from 0 ° C. to 280 ° C. at 20 K / min ["1 .
  • Heating "] then cooled again from 280 ° C to 0 ° C at -10K / min and finally heated again from 20 ° C to 280 ° C at 20K / min [" 2nd heating "].
  • the sample is exposed to high temperatures over a longer period, which leads to side reactions in the case of unstable compounds, in particular to transesterifications in the case of polyalkylene terephthalate blends.
  • the shift of the melting peaks between 1.
  • Heating and heating to lower temperatures can therefore be considered as a measure of the degree of transesterification and thus as a measure of the thermal stability of a sample, wherein a shift of less than or equal to 10 ° C according to the invention represents a slight tendency to transesterification, while a Shift by more 10 ° C for a high degree of transesterification and thus stands for low thermal stability.
  • compositions as well as molding compositions and products to be produced therefrom
  • R 1, R 2 are identical or different and represent a linear or branched CrC 6 - are alkyl and / or C 6 -C 4 aryl,
  • R 3 is linear or branched CrC 10 alkylene, C 6 -C 10 arylene or dC 6 - alkyl-C 6 -C arylene or C 6 -C 0 0 aryl-Ci-C 6 alkylene,
  • M is aluminum, zinc or titanium, m is an integer in the range of 1 to 4; n is an integer in the range from 1 to 3, and x is 1 and 2, where n, x and m in formula (II) can simultaneously only take on such integers that the diphosphinic acid salt of formula (II) as a whole is uncharged,
  • reaction product E) at least one reaction product which differs from component D) from a melamine derivative with phosphoric acids or condensed phosphoric acids.
  • products based on the compositions according to the invention show very high filament ignitability values and flame retardances compared to the prior art and, despite the use of at least two different polyester components - only a slight tendency to transesterification.
  • component D) and component E both high GWIT values and, at the same time, high thermal stability with respect to transesterification can thus be achieved in component-C) flame-retardant polyester mixtures from components A) and B). If at least one of the two components D) and / or E) is missing, increased interesterification of the components A) and B) is obtained with one another, which is proved in the example section by corresponding experiments.
  • alkyl denotes a straight-chain or branched saturated hydrocarbon group
  • an alkyl group having 1 to 6 carbon atoms is used, which may be referred to as a "lower alkyl group”.
  • Preferred alkyl groups are methyl (Me), ethyl (Et), propyl, in particular n-propyl and isopropyl, butyl, in particular n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl groups, in particular n-butyl. Pentyl, iso-pentyl, neo-pentyl, hexyl groups and the like. The same applies to the term polyalkylene.
  • Aryl in the context of the present invention denotes a monocyclic aromatic hydrocarbon ring system or a polycyclic ring system in which two or more aromatic hydrocarbon rings are condensed, or at least one aromatic monocyclic hydrocarbon ring having one or more cycloalkyl and / or cycloheteroalkyl rings
  • aryl or arylene is an aryl group having 6 to 14 carbon atoms
  • Preferred aryl groups having an aromatic carbocyclic ring system are phenyl, 1-naphthyl (bicyclic), 2-naphthyl (bicyclic), anthracenyl (tricyclic), phenanthrenyl (tricyclic
  • Other preferred aryl groups are benzodioxanyl, benzodioxolyl, chromanyl, indolinyl groups and the like
  • aryl groups may be substituted as described herein
  • an aryl group may be substituted with
  • Alkylaryl in the meaning of the present invention means an alkyl-aryl group, wherein the alkylaryl group is covalently bonded to the defined chemical structure by the alkyl group.
  • a preferred alkylaryl group according to the invention is the benzyl group (-CH 2 -C 6 H 5 ).
  • Alkylaryl groups according to the present invention may optionally be substituted, that is, either the aryl group and / or the alkyl group may be substituted.
  • arylalkyl in the context of the present invention means an aryl-alkyl group, wherein the arylalkyl group is covalently bonded to the defined chemical structure by the aryl group.
  • the invention preferably relates to compositions and molding compositions and products to be produced therefrom, based on 100 parts by mass of component A)
  • compositions of the invention for further use are prepared by mixing the components A) to E) to be used as starting materials in at least one mixing tool, preferably a compounder.
  • mixing tool preferably a compounder.
  • molding compositions obtained as intermediates on the compositions according to the invention are obtained.
  • the compositions, but also the molding compositions and products to be prepared therefrom, can either consist exclusively of components A) to E), or else contain further components in addition to components A) to E), preferably at least one of the components F listed below ) to K).
  • compositions according to the invention contain, in addition to the components A) to E) F) at least one further flame retardant, different from the components C), D) and E), preferably in amounts in the range from 2 to 50 parts by mass, based on 100 parts by mass of component A).
  • compositions according to the invention and molding compositions and products to be produced therefrom, in addition to components A) to F) or instead of F), also contain G) at least one metal sulfate, preferably in amounts ranging from 1 to 40 parts by mass, based on 100 parts by mass component A).
  • the compositions according to the invention, as well as molding compositions and products to be produced therefrom additionally comprise H) at least one filler other than components A) to G) or instead of F) and / or G) or at least one filler other than components A) to G) Reinforcement, preferably in amounts ranging from 0.1 to 300 parts by mass, based on 100 parts by mass of component A).
  • compositions according to the invention contain, in addition to the components A) to H) or instead of F) and / or G) and / or H), K) at least one further of the components C) to H) various additive, preferably in amounts ranging from 0.01 to 80 parts by mass, based on 100 parts by mass of component A).
  • the components F), G), H) and K) may be present in the compositions, molding compositions and products, but they may also not be present.
  • the following combinations of the components preferably result for the compositions, molding compositions and products:
  • compositions of the invention which are collectively referred to in the plastics technology as molding compositions, fall during processing the components A) to E) and optionally additionally at least one of the components F), G), H) or K) preferably as granules, in strand form or as a powder.
  • the preparation is carried out by mixing the compositions according to the invention in at least one mixing tool, preferably a compounder, particularly preferably a co-rotating twin-screw extruder.
  • thermoplastic molding compositions can either consist exclusively of components A) to E), or else contain components in addition to components A) to E), preferably at least one of components F) and / or G) and / or H) and / or K).
  • the molding compositions according to the invention are then subjected as a matrix material to injection molding or extrusion, preferably injection molding, in order to produce products according to the invention.
  • Products according to the invention therefore contain the same components A) to E) and optionally additionally at least one of the components F), G), H) or K).
  • the polyalkylene terephthalates or polycycloalkylene terephthalates other than polyethylene terephthalate to be used according to the invention as component A) can be prepared by different processes, synthesized from different building blocks and, in a special case alone or in combination with processing aids, stabilizers, polymeric alloying partners, preferably elastomers, or reinforcing materials mineral fillers or glass fibers, and optionally further additives, to materials with specially selected property combinations are equipped. Blends with proportions of other polymers are also suitable, one or more compatibilizers optionally being able to be used. The properties of the polymers can be improved as needed by adding elastomers.
  • Polyalkylene terephthalates or polycycloalkylene terephthalates to be used preferably as component A) can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 C-atoms produced by known methods (Plastics Handbook, Vol. VIII, p 695 ff, Karl Hanser Verlag, Kunststoff 1973).
  • Polyalkylene terephthalates or polycycloalkylene terephthalates preferably to be used as component A) contain at least 80 mol%, preferably at least 90 mol%, based on the dicarboxylic acid, of terephthalic acid residues and at least 80 mol%, preferably at least 90 mol%, based on the diol component, 1, 4-cyclohexanedimethanol and / or propanediol-1, 3 (in the case of polypropylene terephthalate) and / or butanediol-1, 4-radicals.
  • polyalkylene terephthalates or polycycloalkylene terephthalates which are preferably to be used as component A) may contain up to 20 mol% of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acid radicals having 4 to 12 carbon atoms, especially radicals of phthalic acid, isophthalic acid, naphthalene 2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, cyclohexanedicarboxylic acid.
  • Polyalkylene terephthalates or polycycloalkylene terephthalates which are preferably to be used as component A) can, in addition to 1,4-cyclohexanedimethanol or 1,3-propanediol or 1,4-butanediol-1,4, contain up to 20 mol% of other aliphatic diols having 3 to 12 C atoms or up to 20 mol% cycloaliphatic diols having 6 to 21 carbon atoms, preferably residues of propanediol-1, 3, 2-ethylpropanediol-1, 3, neopentyl glycol, pentane-diol-1, 5, hexanediol-1 .6 , 3-methylpentanediol-2,4, 2-methylpentanediol-2,4,2,2,4-trimethylpentanediol-1,3,3,2,4-trimethylpentanediol-1,2,5-eth
  • Polyalkylene terephthalates or polycycloalkylene terephthalates which are particularly preferably used as component A) are those which are prepared solely from terephthalic acid and its reactive derivatives, in particular their dialkyl esters, and 1,4-cyclohexanedimethanol and / or 1,3-propanediol and / or 1,4-butanediol , particularly preferably poly-1, 4-cyclohexanedimethanol terephthalate, polyethylene terephthalate and polybutylene terephthalate and mixtures thereof.
  • Polyalkylene terephthalates or polycycloalkylene terephthalates which are preferably to be used as component A) are also copolyesters which consist of at least two of the above acid components and / or at least two of the abovementioned alcohol components.
  • Particularly preferred copolyesters are poly (ethylene glycol / butanediol-1, 4) terephthalates.
  • the polyalkylene terephthalates or polycycloalkylene terephthalates to be used as component A) generally have an intrinsic viscosity in the range from 30 to 150 cm 3 / g, preferably in the range from 40 to 130 cm 3 / g, particularly preferably in the range from 50 to 100 cm 3 / g, measured in each case Phenol / o-dichlorobenzene (1: 1 parts by wt.) At 25 ° C.
  • the intrinsic viscosity IV also referred to as Staudinger index or intrinsic viscosity, is proportional to the average molecular mass according to the Mark-Houwink equation and is the extrapolation of the viscosity number VN in the case of vanishing polymer concentrations.
  • the VN [ml / g] is obtained from the measurement of the solution viscosity in the capillary viscometer, for example Ubbelohde viscometer.
  • the solution viscosity is a measure of the average molecular weight of a plastic.
  • the determination is carried out on dissolved polymer, with different solvents (formic acid, m-cresol, tetrachloroethane, phenol, 1, 2-dichlorobenzene, etc) and concentrations are used.
  • the viscosity number VN makes it possible to control the processing and service properties of plastics.
  • Thermal stress on the polymer, aging or exposure to chemicals, weathering and light can be investigated by comparative measurements.
  • the method is standardized for common plastics, in the context of the present invention according to DIN ISO 1628-5 for polyester. See also: http://de.wikipedia.org/wiki/Viskosimetrie and "http://de.wikipedia.org/wiki/Mark-Houwink-Gleichung.”
  • the polyalkylene terephthalates or polycycloalkylene terephthalates to be used according to the invention as component A) may also be used in admixture with other polyesters and / or other polymers.
  • polyalkylene terephthalates or polycycloalkylene terephthalates to be used as component A) may be admixed in the melt during the compounding of conventional additives, in particular mold release agents.
  • the compounding is preferably carried out in extruders, more preferably in co-rotating twin-screw extruders, counter-rotating twin-screw extruders, planetary roller extruders or co-kneaders and includes the process operations conveying, melting, dispersing, mixing, degassing and pressure build-up.
  • PBT Polybutylene terephthalate
  • poly-1,4-cyclohexanedimethanol terephthalate [CAS No. 25037-99-4] is preferably used as polycycloalkylene terephthalate as component A).
  • polyetylenerephthalat [CAS No. 25038-59-9]
  • PET Polyetylenerephthalat
  • PET contains at least 80 mol%, preferably at least 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80 mol%, preferably at least 90 mol%, based on the diol component, ethylene glycol.
  • PET preferably to be used as component B) may contain, in addition to terephthalic acid residues, up to 20 mol% of other aromatic dicarboxylic acids containing 8 to 14 carbon atoms or aliphatic dicarboxylic acids containing 4 to 12 carbon atoms, in particular phthalic acid, isophthalic acid, naphthalene-2 , 6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, cyclohexanedicarboxylic acid, with isophthalic acid being preferred.
  • Particularly preferred is an isophthalic acid content in the range of 0.1 to 10 mol%, most preferably in the range of 0.5 to 5 mol%.
  • PET preferably used as component B
  • PET may contain up to 20 mol% of other aliphatic diols having 3 to 12 C atoms or up to 20 mol%.
  • cycloaliphatic diols having 6 to 21 carbon atoms preferably radicals of propanediol 1, 3, 2-ethylpropanediol-1, 3, neopentyl glycol, pentane-diol-1, 5, hexanediol-1 .6, 3-methylpentanediol-2, 4,2-methylpentanediol-2,4,2,2,4-trimethylpentanediol-1,3,3,2,4,4-trimethylpentanediol-1,2,5-ethylhexanediol 1,3,2,2-diethylpropanediol-1, 3, hexanediol-2,5, 1,4-di ( ⁇ -hydroxyethoxy) benzene, 2,
  • PET is particularly preferably used, which is prepared solely from terephthalic acid and its reactive derivatives, in particular their dialkyl esters and ethylene glycol.
  • PET to be used according to the invention as component B) generally has an intrinsic viscosity in the range from 30 to 150 cm 3 / g, preferably in the range from 40 to 130 cm 3 / g, particularly preferably in the range from 50 to 100 cm 3 / g in each case in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
  • the PET to be used according to the invention may also be recycled material.
  • Post Industrial Recyclate also called Pre Consumer Recyclate
  • this is production waste in the polycondensation, in the compounding (eg offspec-goods) or in processing z.
  • PET recyclates from recycled PET bottles are preferably obtained by a method according to DE 103 24 098 A1, WO 2004/009315 A1 or WO 2007/116022 A2.
  • the PET to be used as component B) can during the compounding customary additives, in particular mold release agents, be mixed in the melt.
  • a PET with 0.5 to 5 mol% [based on 100 mol% of diacid] isophthalic acid is particularly preferably used.
  • organic phosphinic salts of the abovementioned formula (I) and / or organic diphosphinic acid salts of the abovementioned formula (II) and / or their polymers to be used according to the invention as component C) are also referred to as phosphinates in the context of the present invention.
  • M in the formulas (I) or (II) is aluminum.
  • R 1 , R 2 in the formulas (I) and (II) are identical or different and denote C 1 -C 6 -alkyl, linear or branched and / or phenyl.
  • R 1 , R 2 are particularly preferably identical or different and are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.
  • R 3 in formula (II) is preferably methylene, ethylene, N-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, Ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene, phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.
  • R 3 is phenylene or naphthylene.
  • Suitable phosphinates are described in WO-A 97/39053, the content of which with respect to the phosphinates is included in the present application.
  • Particularly preferred phosphinates for the purposes of the present invention are aluminum and zinc salts of dimethylphosphinate, ethylmethylphosphinate, diethylphosphinate and methyl-n-propylphosphinate, and mixtures thereof.
  • m in formula (I) is 2 and 3, more preferably 3.
  • n in formula (II) is 1 and 3, more preferably 3.
  • x in formula (II) is 1 and 2, more preferably 2.
  • component C) is an unfusible metal phosphinate, i. H. that the metal phosphinate decomposes before reaching the melting point.
  • component C aluminum tris (diethylphosphinate) [CAS No. 225789-38-8] is used, the z. B. from the Fa. Clariant International Ltd. Muttenz, Switzerland is marketed under the trade name Exolit ® OP1230 or OP1240 Exolit ®.
  • At least one condensed melamine derivative is used.
  • Preferred condensation products of the melamine are melam [CAS No. 3576- 88-3], Meiern [CAS No. 1502-47-2] or melon [CAS No. 32518-77-7], and mixtures thereof.
  • dicyandiamide is formed from cyanamide or ammonium dicyanamide, which then cyclizes to melamine. Condensation of melamine leads to release ammonia directly or via the intermediate melam to the target compound.
  • Meiern is particularly preferable to use Meiern as component D, with melem grades having a melamine content of less than 1.0% by weight being very particularly preferred, and the content of melamine being determined by NIR-FT-IR.
  • Meiern is offered for example as Delacal ® NFR by the company. Delamin Ltd., Derby, UK.
  • compositions and molded articles or products to be produced therefrom comprise at least one reaction product of a melamine derivative other than component D) with phosphoric acids or condensed phosphoric acids and mixtures thereof.
  • Melamine derivatives which are preferably to be used in component E) here are melamine, condensation products of melamine, in particular Meiern, melam or melon, and also derivatives of these compounds, in particular their nitrogen-substituted species.
  • phosphoric acids or condensed phosphoric acids according to the invention are in particular phosphoric acid, diphosphoric acid, meta- and polyphosphoric acid.
  • Preferred reaction products of melamine derivatives to be used as component E) with phosphoric acids or condensed phosphoric acids are dimelamine phosphate, dimelamine pyrophosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melampolyphosphate, melon polyphosphate and melem polyphosphate, as they are z.
  • component E) is melamine polyphosphate.
  • Melamine polyphosphate is commercially available in various product qualities. Examples include Melapur ® 200/70 (Fa. BASF, Ludwigshafen, Germany) and Budit ® 3141 (Fa. Budenheim, Budenheim, Germany).
  • the flame retardants to be used as component F) in a preferred embodiment of the compositions according to the invention and to be produced therefrom or products thereof are preferably halogen-free.
  • nitrogen-containing flame retardants are used as component F).
  • melamine cyanurate bis-melamine-zinc diphosphate (EP 2 609 173 A1) and / or bis-melamine alumotriphosphate (EP 2 609 173 A1)
  • melamine cyanurate is particularly particularly preferred.
  • An example of this is u.a. Melapur® MC25 from BASF, Ludwigshafen, Germany.
  • Further nitrogen-containing flame retardants other than components D) and E) to be used as component F) are the reaction products of trichlorotriazine, piperazine and morpholine according to CAS No. 1078142-02-5, in particular MCA PPM triazine HF from MCA Technologies GmbH, Biel-Benken, Switzerland.
  • phosphorus-containing flame retardants used as component F).
  • the phosphorus-containing flame retardants used as component F) different from the components C) and E) are preferably phosphorus-containing compounds from the group of inorganic metal phosphinates, in particular aluminum phosphinate and zinc phosphinate, the mono- and oligomeric phosphoric and phosphonic acid esters, in particular triphenyl phosphate (TPP), Resorcinol bis (diphenyl phosphate) (RDP), bisphenol A bis diphenyl phosphate (BDP) including oligomers, polyphosphonates, in particular bisphenol A diphenyl methyl phosphonate copolymers such.
  • TPP triphenyl phosphate
  • RDP Resorcinol bis (diphenyl phosphate)
  • BDP bisphenol A bis diphenyl phosphate
  • Eg Nofia TM HM1 100 [CAS-No. 68664-06-2] from FRX Polymers, Chelmsford, USA), and derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxides (DOPO derivatives)], phosphonateamines, metal phosphonates, in particular aluminum phosphonate and zinc phosphonate, phosphine oxides and phosphazenes.
  • DOPO derivatives 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxides
  • phenoxyphosphazene oligomers Particularly preferred are phenoxyphosphazene oligomers.
  • the phosphazenes and their preparation are z.
  • component F ring-shaped phenoxyphosphazenes such as 2,2,4,4,6,6-hexahydro-2,2,4,4,6,6-hexaphenoxytriazatriphosphorines [CAS No. 1 184-10-7] and / or such as z.
  • Rabitle® FP1 10 [CAS-No. 1203646-63-2] are available.
  • component F flame retardants or flame retardant synergists not specifically mentioned here can also be used as component F). These also include purely inorganic phosphorus compounds other than component E), in particular red phosphorus or boron phosphate hydrate. Furthermore, it is also possible to use mineral flame retardant additives or salts of aliphatic and aromatic sulfonic acids, in particular metal salts of perfluorobutanesulfonic acid.
  • Flammschutzstoffsynergisten also come from the group of oxygen, nitrogen or sulfur-containing metal compounds different from component G), wherein metal is zinc, molybdenum, calcium, titanium, magnesium or boron, preferably zinc oxide, zinc borate, zinc stannate, zinc hydroxystannate, zinc sulfide, molybdenum oxide , Magnesium carbonate, calcium carbonate, calcium oxide, titanium nitride, boron nitride, magnesium nitride, zinc nitride, calcium borate, magnesium borate or mixtures thereof.
  • metal is zinc, molybdenum, calcium, titanium, magnesium or boron, stannate, zinc hydroxystannate, zinc sulfide, molybdenum oxide , Magnesium carbonate, calcium carbonate, calcium oxide, titanium nitride, boron nitride, magnesium nitride, zinc nitride, calcium borate, magnesium borate or mixtures thereof.
  • Suitable flame retardant additives to be used as component F) are carbon formers, particularly preferably poly (2,6-diphenyl-1,4-phenyl) ether, in particular poly (2,6-dimethyl-1,4-phenylene) ether [CAS No. 25134-01 -4], phenol-formaldehyde resins, polycarbonates, polyimides, polysulfones, polyethersulfones or polyether ketones.
  • the flame retardants to be used as component F) can be added in pure form, as well as via masterbatches or compactates of component A) and / or component B).
  • At least one metal sulfate is used, wherein the metal is selected from magnesium, calcium, barium and zinc.
  • magnesium or barium is used, particularly preferably barium.
  • Barium sulphate [CAS No. 7727-43-7] can be used in the form of the naturally occurring barite or in the form of barium sulphate prepared synthetically by known technical processes. As common production methods for barium sulfate, for example, the precipitation of barium sulfide or barium chloride with sodium sulfate is taught in http://de.wikipedia.org/wiki/Bariumsulfat.
  • the average particle size [d50 value] is preferably in the range from 0.1 to 50 ⁇ m, particularly preferably in the range from 0.5 to 10 ⁇ m, and very particularly preferably in the range from 0.6 to 2 ⁇ m.
  • the barium sulfate may be untreated or equipped with inorganic and / or organic surface treatments. Examples of inorganic or organic surface treatments and methods for their application to the surface are taught, for example, in WO2008 / 023074 A1.
  • Suitable synthetic barium sulfates are z. B. from the Fa. Sachtleben Chemie GmbH, Duisburg, Germany under the trade names Blanc fixe F and Blanc Fixe Super F offered.
  • the underlying standard is ISO 13317-3.
  • Further suitable Bariumsulfatoughoughough are z. B. Albasoft® 90 and / or Albasoft® 100 from Deutsche Baryt Industrie Rudolf Alberti GmbH & Co. KG, Bad Lauterberg in the Harz, Germany.
  • the compositions and molding compositions and products to be produced therefrom may contain at least one filler or reinforcing agent. However, preference is also given to a mixture of two or more different fillers and / or reinforcing materials.
  • At least one filler and / or reinforcing material from the group mica, silicate, quartz, especially quartz, titanium dioxide, wollastonite, Nephelinsyenit, kaolin, amorphous silicas, magnesium carbonate, chalk, feldspar, glass fibers, glass beads, glass powder and / or fibrous fillers and / or reinforcing materials based on carbon fibers used as component H).
  • mineral particulate fillers based on mica, silicate, quartz, wollastonite, kaolin, amorphous silicas, magnesium carbonate, chalk or feldspar.
  • needle-shaped mineral fillers are also used with particular preference as an additive.
  • nadeiförmige mineral reinforcing materials also referred to as fillers
  • the mineral has a length: diameter ratio in the range of 2: 1 to 35: 1, more preferably in the range of 3: 1 to 19: 1, most preferably in the range of 4: 1 to 12: 1.
  • the mean particle size d50 of the acicular minerals to be used according to the invention as component H) is preferably less than 20 ⁇ m, more preferably less than 15 ⁇ m, particularly preferably less than 10 ⁇ m.
  • All fillers and / or reinforcing materials to be used as component H) may have a smaller d97 or d50 value than the fillers or reinforcing materials or glass fibers originally used as a result of the processing into the molding compound or to a product.
  • d50 and d97 values in this application their determination and their significance, reference is made to Chemie Ingenieurtechnik (72) pp. 273-276, 3/2000, Wiley-VCH Verlags GmbH, Weinheim, 2000, according to which the d50 value is the particle size below which 50% of the particle quantity is (median value) and the d97 value is that particle size below which 97% of the particle quantity is.
  • the details of the particle size distribution or the particle sizes in the context of the present invention refer to so-called surface-based particle sizes, in each case before incorporation into the thermoplastic molding composition.
  • Particle size determination is by laser diffractometry, see CM. Keck, Modern Pharmaceutical Technology 2009, Freie (2015) Berlin, Chapter 3.1. or QUANTACHROME PARTICULAR WORLD NO 6, June 2007, pages 1 to 16.
  • the underlying standard is ISO 13317-3.
  • the fillers and reinforcing materials can be used individually or as a mixture of two or more different fillers and / or reinforcing materials.
  • the filler and / or reinforcing material to be used as component H) may be surface-modified in a preferred embodiment, particularly preferably with an adhesion promoter or adhesion promoter system, more preferably epoxy-based. However, pretreatment is not essential.
  • glass fibers are used as component H).
  • cut fibers also called short fibers, with a length in the range of 0.1 to 1 mm
  • long fibers with a length in the range of 1 to 50mm
  • continuous fibers with a length L> 50mm
  • Short fibers are made by injection molding used and can be processed directly with an extruder.
  • Long fibers can also be processed in extruders. They are widely used in fiber spraying. Long fibers are often added to thermosets as a filler.
  • Continuous fibers are used as rovings or fabrics in fiber-reinforced plastics. Products with continuous fibers achieve the highest stiffness and strength values.
  • ground glass fibers are offered whose length after grinding is typically in the range of 70 to 200 ⁇ m.
  • Preference according to the invention as component H) cut long glass fibers having an initial length in the range of 1 to 50 mm, more preferably in the range of 1 to 10mm, most preferably used in the range of 2 to 7mm.
  • the initial length refers to the average length of the glass fibers as present before compounding the composition (s) of the invention to a molding composition. Due to the processing, in particular compounding, to the molding compound or to the product in the molding compound or in the article, the glass fibers preferably to be used as component H) can have a smaller d97 or d50 value than the glass fibers originally used. Thus, the arithmetic mean of the glass fiber length after processing is often only in the range of 150 ⁇ and 300 ⁇ .
  • the determination of the glass fiber length and glass fiber length distribution in the context of the present invention in the case of processed glass fibers in analogy to ISO 22314, which initially provides an ashing of the samples at 625 ° C. Subsequently, the ash is placed on a covered with demineralized water slide in a suitable crystallizing and the ashes distributed without effect of mechanical forces in the ultrasonic bath. The next step involves drying in an oven at 130 ° C and then using optical micrographs to determine the fiber length. For this purpose, at least 100 glass fibers are measured from three images, so that a total of 300 glass fibers are used to determine the length.
  • l c and ⁇ are special characteristics of the normal distribution; l c is the mean value and ⁇ is the standard deviation (see: M. Schossig, damage mechanisms in fiber-reinforced plastics, 1, 2011, Vieweg and Teubner Verlag, page 35, ISBN 978-3-8348-1483-8).
  • glass fibers not embedded in a plastic matrix are analyzed for their lengths according to the above methods without the ashing and separation treatment of the ash.
  • the glass fibers [CAS No. 65997-17-3)] preferably to be used according to the invention as component H) preferably have a fiber diameter in the range from 7 to 18 ⁇ m, particularly preferably in the range from 9 to 15 ⁇ m, which can be achieved by at least one option available to the person skilled in the art is to be determined, in particular to be determined by ⁇ -X-ray computed tomography in analogy to "Quantitative measurement of fiber lengths and distribution in fiber-reinforced plastic parts by means of ⁇ -X-ray computed tomography", J. KASTNER, et al DGZfP Annual Meeting 2007 - Lecture 47.
  • the preferably used as component H) glass fibers are preferably added as continuous fibers or as cut or ground glass fibers.
  • the fillers and / or reinforcing materials, in particular glass fibers, to be used as component H) are preferably provided with a suitable sizing system and an adhesion promoter or adhesion promoter system, particularly preferably silane-based.
  • silane compounds of the general formula (III) are silane compounds of the general formula (III)
  • X NH 2 -, HO-, q: an integer from 2 to 10, preferably from 3 to 4, r: an integer from 1 to 5, preferably from 1 to 2, k: an integer from 1 to 3, preferably 1.
  • adhesion promoters are silane compounds from the group of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
  • the silane compounds are preferably used in amounts in the range from 0.05 to 2% by weight, more preferably in the range from 0.25 to 1.5% by weight and in particular in the range from 0.5 to 1 % By weight, based on 100% by weight, of the filling or reinforcing substance, in particular the glass fibers, used for surface coating.
  • Preferred additives to be used as component K) are lubricants and mold release agents, UV stabilizers, colorants, chain-extending additives, antioxidants, plasticizers, flow aids, heat stabilizers, antioxidants, gamma ray stabilizers, hydrolysis stabilizers, elastomer modifiers, antistatic agents, emulsifiers, nucleating agents, processing aids, anti-dripping agents and as far as its use requires, also halogen-containing flame retardants and their synergists.
  • the additives can be used alone or in admixture or in the form of masterbatches.
  • Preferred lubricants and mold release agents are those selected from the series of long-chain fatty acids, the salts of long-chain fatty acids, the ester derivatives of long-chain fatty acids and montan waxes.
  • Preferred long-chain fatty acids are stearic acid or behenic acid.
  • Preferred salts of the long-chain fatty acids are Ca or Zn stearate.
  • Preferred Esterderivate long chain fatty acids are those based on pentaerythritol, especially C 6 -C 8 fatty acid ester of pentaerythritol [CAS no. 68604-44-4] or [CAS no. 16-93-4 851].
  • Montan waxes for the purposes of the present invention are mixtures of straight-chain, saturated carboxylic acids having chain lengths of 28 to 32 C atoms.
  • Lubricants and / or mold release agents from the group of esters of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms with aliphatic saturated alcohols having 2 to 40 carbon atoms and metal salts of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 ° C. are particularly preferred according to the invention are used, with pentaerythritol tetrastearate, calcium stearate [CAS No. 1592-23-0] and / or ethylene glycol dimontanate, in particular Licowax® E [CAS No. 74388-22-0] from Clariant, Muttenz, Basel, being very particularly preferred and pentaerythritol tetrastearate [CAS No. 1 15-83-3] e.g. B. available as Loxiol® P861 Fa. Emery Oleochemicals GmbH, Dusseldorf, Germany is particularly particularly preferred.
  • Substituted resorcinols, salicylates, benzotriazoles, triazine derivatives or benzophenones are preferably used as UV stabilizers.
  • the colorants used are preferably organic pigments, preferably phthalocyanines, quinacridones, perylenes and dyes, preferably nigrosine or anthraquinones, furthermore inorganic pigments, in particular titanium dioxide (if not already used as filler), ultramarine blue, iron oxide, zinc sulfide or carbon black.
  • Titanium dioxide pigments which may be prepared by the sulfate (SP) or chloride (CP) process and which have the anatase and / or rutile structure, preferably rutile structure, are suitable for the titanium dioxide which is preferably used as pigment according to the invention.
  • the main body need not be stabilized, but a special stabilization is preferred: in the case of the CP base body by an Al doping of 0.3-3.0 wt .-% (calculated as Al 2 0 3 ) and an excess of oxygen in the gas phase at the oxidation of titanium tetrachloride to titanium dioxide of at least 2%; in the SP base body by doping z. B. with Al, Sb, Nb or Zn.
  • Titanium dioxide As a white pigment in paints and varnishes, plastics, etc., it is known that unwanted photocatalytic reactions produced by UV absorption lead to the decomposition of the pigmented material. Titanium dioxide pigments absorb light in the near ultraviolet range, creating electron-hole pairs that generate highly reactive radicals on the titanium dioxide surface. The radicals formed in organic media result in a binder degradation. According to the invention, to lower the photoactivity of the titanium dioxide, it is preferably after-treated inorganic, more preferably with oxides of Si and / or Al and / or Zr and / or by the use of Sn compounds.
  • the surface of pigmentary titanium dioxide is preferably covered with amorphous precipitates of oxide hydrates of the compounds SiO 2 and / or Al 2 O 3 and / or zirconium oxide.
  • the Al 2 O 3 sheath facilitates pigment dispersion in the polymer matrix, the Si0 2 sheath impedes the charge exchange on the pigment surface and thus prevents polymer degradation.
  • the titanium dioxide is preferably provided with hydrophilic and / or hydrophobic organic coatings, in particular with siloxanes or polyalcohols.
  • Titanium dioxide [CAS No. 13463-67-7] preferably used as colorant of component K) preferably has an average particle size d50 in the range from 90 to 2000 nm, particularly preferably in the range from 200 to 800 nm.
  • the mean particle size d50 is the value determined from the particle size distribution, to which 50% by weight of the particles have an equivalent spherical diameter smaller than this d50 value.
  • the underlying standard is ISO 13317-3.
  • the details of the particle size distribution or the average particle size in the case of titanium dioxide relate to so-called surface-based particle sizes, in each case before incorporation into the thermoplastic molding composition.
  • the particle size determination is carried out according to the invention by laser diffractometry, see CM. Keck, Modern Pharmaceutical Technology 2009, Freie (2015) Berlin, Chapter 3.1. or QUANTACHROME PARTICLE WORLD NO 6, June 2007, pages 1 to 16.
  • Commercially available titanium dioxide are, for example, Kronos® 2230, Kronos® 2233, Kronos® 2225 and Kronos® vlp7000 from Kronos, Dallas, USA.
  • the titanium dioxide preferably to be used as the pigment is preferably used in the range from 0.1 to 60 parts by mass, particularly preferably in the range from 1 to 35 parts by mass, very particularly preferably in the range from 2 to 20 parts by mass, based in each case on 100 parts by mass of component A).
  • component K it is possible to use di- or polyfunctional branching or chain-extending additives containing at least two and at most 15 branching or chain-extending functional groups per molecule.
  • Suitable branching or chain-extending additives are low molecular weight or oligomeric compounds which have at least two and at most 15 branching or chain-extending functional groups per molecule which can react with primary and / or secondary amino groups and / or amide groups and / or carboxylic acid groups
  • chain-extending active functional groups are preferably isocyanates, alcohols, blocked isocyanates, epoxides, maleic anhydride, oxazolines, oxazines, oxazolones.
  • Particularly preferred difunctional or polyfunctional branching or chain-extending additives are diepoxides based on diglycidyl ether (bisphenol and epichlorohydrin), based on amine epoxy resin (aniline and epichlorohydrin), based on diglycidyl esters (cycloaliphatic dicarboxylic acids and epichlorohydrin) individually or in mixtures and also 2,2 Bis [p-hydroxy-phenyl] -propane-diglycidyl ether, bis [p- (N-methyl-N-2,3-epoxy-propylamino) -phenyl] -methane and epoxidized fatty acid esters of glycerol containing at least two and at most 15 epoxide groups per molecule.
  • diglycidyl ether bisphenol and epichlorohydrin
  • amine epoxy resin aniline and epichlorohydrin
  • diglycidyl esters cycloaliphatic dicarboxylic acids and epichloro
  • Particularly preferred difunctional or polyfunctional branching or chain-extending additives are glycidyl ethers, very particularly preferably bisphenol A diglycidyl ether [CAS No. 98460-24-3] or epoxidized fatty acid esters of glycerol, and also most preferably epoxidized soybean oil [CAS No. 8013- 07-8].
  • Poly- or oligoglycidyl or poly (.beta.-methylglycidyl) ethers obtainable by reacting a compound having at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups and a suitably substituted epichlorohydrin under alkaline conditions, or in the presence of an acidic catalyst and subsequent alkali treatment
  • Poly- or oligoglycidyl or poly (.beta.-methylglycidyl) ethers are preferably derived from acyclic alcohols, in particular ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol, poly (oxypropylene ) -glycols, propane-1,3-diol, butane-1,4-diol, poly (oxytetramethylene) -glycols, pentane-1,5-diol, hex
  • cycloaliphatic alcohols in particular 1,3-dihydroxycyclohexane, 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) -propane or 1, 1-bis (hydroxymethyl) cyclohex-3-ene or they have aromatic nuclei, in particular N, N-bis (2-hydroxyethyl) aniline or ⁇ , ⁇ '-bis (2-hydroxyethylamino) diphenylmethane.
  • the epoxide compounds may preferably also be derived from mononuclear phenols, in particular from resorcinol or hydroquinone, or they are based on polynuclear Phenols, in particular bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane, 4, 4'-Dihydroxydiphenylsulfon or obtained under acidic conditions condensation products of phenols with formaldehyde, in particular phenol novolacs. 2.
  • Poly- or Oligo- (N-glycidyl) compounds also obtainable by dehydrochlorinating the reaction products of epichlorohydrin with amines containing at least two amino hydrogen atoms.
  • amines are preferably aniline, toluidine, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane, but also ⁇ , ⁇ , ⁇ -triglycidyl-m -aminophenyl or ⁇ , ⁇ , ⁇ -triglycidyl-p-aminophenol.
  • the poly (N-glycidyl) compounds also preferably include ⁇ , ⁇ '-diglycidyl derivatives of cycloalkylene ureas, particularly preferably ethyleneurea or 1, 3-propyleneurea, and ⁇ , ⁇ '-diglycidyl derivatives of hydantoins, in particular 5,5-dimethylhydantoin , 3.
  • poly- or oligo- (S-glycidyl) compounds in particular di-S-glycidyl derivatives which are derived from dithiols, preferably ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether.
  • Epoxidized fatty acid esters of glycerol in particular epoxidized vegetable oils. They are obtained by epoxidizing the reactive olefin groups of triglycerides of unsaturated fatty acids.
  • the preparation of epoxidized fatty acid esters of glycerol can be carried out starting from unsaturated fatty acid esters of glycerol, preferably of vegetable oils, and organic peroxycarboxylic acids (Prileschajew reaction). Methods of making epoxidized vegetable oils are described, for example, in Smith, March, March's Advanced Organic Chemistry (5th Ed., Wiley-Interscience, New York, 2001).
  • Preferred epoxidized fatty acid esters of glycerol are vegetable oils.
  • Epoxidized fatty acid ester of glycerol which is particularly preferred according to the invention is epoxidized soybean oil [CAS No. 8013-07-8].
  • Glycidyl methacrylate modified styrene-acrylate polymers obtainable by polymerization of styrene, glycidyl methacrylate and acrylic acid and / or methacrylic acid.
  • Softeners to be used preferably as component K) are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils or N- (n-butyl) benzenesulfonamide.
  • Preferred flow agents used as component K) are copolymers of at least one ⁇ -olefin with at least one methacrylic acid residue or acrylic ester of an aliphatic alcohol.
  • copolymers in which the oc-olefin is composed of ethene and / or propene and the Methacrylkla rester or acrylic ester as the alcohol component contains linear or branched alkyl groups having 6 to 20 carbon atoms. Very particular preference is given to acrylic acid (2-ethyl) hexyl ester. Copolymers which are suitable according to the invention as flow aids are notable, apart from the composition, also for their low molecular weight. Accordingly, preference is given above all to copolymers which have an MFI value measured at 190 ° C.
  • the MFI Melt Flow Index
  • the MFI or all information on the MFI in the context of the present invention relate or have become uniform ISO 1 133 measured at 190 ° C and a test weight of 2.16 kg.
  • Preferred according to the invention are copolymers of an ⁇ -olefin with an acrylic ester of an aliphatic alcohol. Particular preference is given to a copolymer of ethene and 2-ethylhexyl acrylate alone.
  • Elastomeric modifiers to be used preferably as component K) include inter alia one or more graft polymers of
  • the graft K.2 generally has an average particle size (d50 value) in the range of 0.05 to 10 ⁇ , preferably in the range of 0.1 to 5 ⁇ , more preferably in the range of 0.2 to 1 ⁇ .
  • Monomers K.1 are preferably mixtures of
  • K.1.11 50 to 99% by weight of vinylaromatics and / or ring-substituted vinylaromatics, in particular styrene, oc-methylstyrene, p-methylstyrene, p-chlorostyrene, and / or methoxy acrylic acid (C 1 -C 8 ) alkyl esters, in particular methyl methacrylate, ethyl methacrylate and
  • K.1.2 from 1 to 50% by weight of vinyl cyanides, in particular unsaturated nitriles such as acrylonitrile and methacrylonitrile, and / or (meth) acrylic acid (C 1 -C 8 ) -alkyl esters, in particular methyl methacrylate, glycidyl methacrylate, n-butyl acrylate, Butyl acrylate, and / or derivatives, in particular anhydrides and imides of unsaturated carboxylic acids, in particular maleic anhydride or N-phenyl-maleimide.
  • unsaturated nitriles such as acrylonitrile and methacrylonitrile
  • acrylic acid (C 1 -C 8 ) -alkyl esters in particular methyl methacrylate, glycidyl methacrylate, n-butyl acrylate, Butyl acrylate, and / or derivatives, in particular anhydrides and imides of unsaturated carboxylic acids, in particular male
  • Preferred monomers K.1.1 are selected from at least one of the monomers styrene, oc-methylstyrene and methyl methacrylate
  • preferred monomers K.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride, glycidyl methacrylate and methyl methacrylate.
  • Particularly preferred monomers are K.1.1 styrene and K.1.2 acrylonitrile.
  • Suitable graft bases K.2 for the graft polymers to be used in the elastomer modifiers are, for example, diene rubbers, EPDM rubbers, ie those based on ethylene / propylene and optionally diene, furthermore acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.
  • EPDM stands for ethylene-propylene-diene rubber.
  • Preferred grafting bases K.2 are diene rubbers, in particular based on butadiene, isoprene, etc., or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers, in particular according to K.1.1 and K.1.2, with the proviso that the glass transition temperature of component K.2 is ⁇ 10 ° C., preferably ⁇ 0 ° C., more preferably ⁇ -10 ° C.
  • Particularly preferred graft bases K.2 are ABS polymers (emulsion, bulk and suspension ABS) wherein ABS stands for acrylonitrile-butadiene-styrene, as described for.
  • ABS acrylonitrile-butadiene-styrene
  • the elastomer modifiers or graft polymers are free-radical
  • Polymerization preferably by emulsion, suspension, solution or
  • graft rubbers are also ABS polymers which are prepared by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.
  • graft polymers according to the invention are also understood as those products which are obtained by (co) polymerization of the grafting monomers in the presence of the grafting base and are obtained during the workup.
  • suitable acrylate rubbers are based on graft bases K.2 which are preferably polymers of alkyl acrylates, optionally with up to 40% by weight, based on K.2 of other polymerizable, ethylenically unsaturated monomers.
  • Preferred polymerizable acrylic acid esters include C 1-8 alkyl esters, preferably methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halogen-C 1 -C 8 -alkyl esters, preferably chloroethyl acrylate, glycidyl esters and mixtures of these monomers.
  • graft polymers with butyl acrylate as core and methyl methacrylates as shell in particular Paraloid® EXL2300, Dow Coming Corporation, Midland Michigan, USA, are particularly preferred.
  • Suitable grafting bases according to K.2 are silicone rubbers having graft-active sites, as described in DE-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 3 631 539.
  • Preferred graft polymers having a silicone moiety are those which comprise methyl methacrylate or styrene-acrylonitrile as shell and a silicone / acrylate graft as core.
  • styrene-acrylonitrile shell may, for. Metablen ® SRK200.
  • methyl methacrylate shell may, for. B. ® Metablen S2001, Metablen S2030 ® and / or Metablen SX-005 ® be used.
  • Metablen® ® is particularly preferred S2001.
  • the products with the trade name Metablen® ® are available from Mitsubishi Rayon Co., Ltd., Tokyo, Japan.
  • crosslinking monomers having more than one polymerizable double bond can be copolymerized.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 C atoms and unsaturated monohydric alcohols having 3 to 12 C atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 C atoms, preferably ethylene glycol dimethacrylate, allyl methacrylate ; multiple unsaturated heterocyclic compounds, preferably trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, preferably di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least 3 ethylenically unsaturated groups.
  • crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
  • the amount of the crosslinked monomers is preferably 0.02 to 5 wt .-%, in particular 0.05 to 2 wt .-%, based on 100 wt .-% of the graft K.2.
  • cyclic crosslinking monomers having at least 3 ethylenically unsaturated groups it is advantageous to limit the amount to less than 1% by weight, based on 100% by weight, of the grafting base K.2.
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which may optionally be used in addition to the acrylic acid esters for the preparation of the graft K.2 are acrylonitrile, styrene, oc-methylstyrene, acrylamides, vinyl-CrC 6 -alkyl ether, methyl methacrylate, glycidyl methacrylate, butadiene.
  • Preferred acrylate rubbers as grafting base K.2 are emulsion polymers which have a gel content of at least 60% by weight.
  • graft polymer-based elastomer modifiers which have glass transition temperatures ⁇ 10 ° C., preferably ⁇ 0 ° C., particularly preferably ⁇ -20 ° C., can likewise be used.
  • Thermostabilizers which are preferably used as component K) are selected from the group of sulfur-containing stabilizers, in particular sulfides, dialkylthiocarbamates or thiodipropionic acids, as well as those selected from the group of iron salts and copper salts, in particular copper (I) iodide, which are preferably in combination with potassium iodide and / or sodium hypophosphite NaH 2 P0 2 are used or, furthermore, sterically hindered amines, in particular Tetrametyhlpiperidin derivatives, aromatic secondary amines, in particular Diphenylamines, hydroquinones, substituted resorcinols, salicylates, benzotriazoles and benzophenones, as well as sterically hindered phenols and aliphatically or aromatically substituted phosphites and various substituted representatives of these groups.
  • sulfur-containing stabilizers in particular sulfides, dialkylthiocarbamates or
  • sterically hindered phenols preference is given to using those having at least one 3-tert-butyl-4-hydroxy-5-methylphenyl and / or at least one 3,5-di- (tert-butyl-4-hydroxyphenyl) building block , wherein 1, 6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] [CAS No. 35074-77-2] (Irganox® 259 Fa. BASF SE , Ludwigshafen, Germany), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] [CAS No.
  • ADK Stab® AO 80 is particularly preferred.
  • ADK Stab® AO 80 is a commercial product of Adeka-Palmerole SAS, Mulhouse, France.
  • aliphatically or aromatically substituted phosphites is preferably bis (2,4-dicumylphenyl) -pentaerythritol-diphosphite [CAS No. 154862-43-8], z. From Dover Chemical Corp., Dover, USA, under the trade name Doverphos® S9228, and tetrakis (2,4-di-tert-butylphenyl) -1, 1-biphenyl-4,4'-diylbisphosphonite [CAS No. 38613-77-3] used, the z. B. as Hostanox® P-EPQ from Clariant International Ltd., Muttenz, Switzerland can be obtained.
  • component K) for protection against basic hydrolysis inorganic phosphate salts from the group of Metallhydrogenphosphate, the Metalldihydrogenphosphate, the Metalldihydrogenpyrophosphate and / or the metal pyrophosphates, wherein metal here for sodium, potassium, magnesium, calcium, zinc, copper and / or aluminum stands.
  • the corresponding hydrates are also included.
  • such inorganic phosphate salts are used which have a pH in the range of 2 to 6, more preferably in the range of 2 to 4, wherein the information on the pH here on aqueous medium at 20 ° C and a concentration of 1 g per liter.
  • metal dihydrogen pyrophosphates and the metal pyrophosphates it is preferred to use sodium dihydrogen pyrophosphate [CAS No. 7758-16-9], calcium dihydrogen pyrophosphate [CAS No. 14866-19-4], magnesium pyrophosphate [CAS No. 13446-24-7], calcium pyrophosphate [CAS No 7790-76-3] and zinc pyrophosphate [CAS No. 7446-26-6].
  • metal hydrogen phosphates are preferably calcium hydrogen phosphate [CAS No. 7757-93-9], calcium hydrogen phosphate dihydrate [CAS No.7789-77-7], magnesium hydrogen phosphate [CAS No. 7757-86-0] and Zinc hydrogen phosphate [CAS No.
  • metal dihydrogen phosphates which are particularly preferably used, preference is given to aluminum dihydrogenphosphate [CAS No. 13530-50-2], magnesium bis (dihydrogenphosphate) [CAS No. 13092-66-5], calcium bis (dihydrogenphosphate) [CAS no. No. 7758-23-8], zinc bis (dihydrogen phosphate) [CAS No. 13584-37-3] and zinc bis (dihydrogen phosphate) dihydrate [CAS No. 13986-21 -5].
  • Nucleating agents which are preferably used as component K) are sodium or calcium phenylphosphinate, aluminum oxide, silicon dioxide or talc [CAS No. 14807-96-6], with talc being preferred. Microcrystalline talc is particularly preferably used.
  • Talc also referred to as talc, is a layered silicate with the chemical composition Mg 3 [Si 4 O 10 (OH) 2 ], which, depending on the modification, crystallizes as talc 1 A in the triclinic or as talc 2M in the monoclinic crystal system (http: //de.wikipedia.org/wiki/Talkum).
  • Talcum [CAS No. 14807-96-6] to be used according to the invention can be obtained, for example, as Mistron® R10 from Imerys Tale Group, Toulouse, France (Rio Tinto Group).
  • Anti-dripping agents which are preferably used as component K) are, in particular, tetrafluoroethylene polymers.
  • the tetrafluoroethylene polymers can be used in pure form or else in combination with other resins, preferably styrene-acrylonitrile (SAN), or acrylates, preferably methyl methacrylate or butyl acrylate.
  • SAN styrene-acrylonitrile
  • a particularly preferably suitable example of tetrafluoroethylene-styrene-acrylonitrile resins is z.
  • B. cycolac ® INP 449 [CAS No 1427364-85-9.] Of the company Sabic Corp., Riyadh, Saudi Arabia.
  • a particularly preferably suitable example of tetrafluoroethylene-acrylate resins is z.
  • Anti-drip agents comprising tetrafluoroethylene polymers are used according to the invention as component K), preferably in amounts ranging from 0.01 to 5 parts by mass, more preferably in the range from 0.05 to 2 mass parts, based in each case on 100 mass fractions of component A).
  • halogen-containing flame retardants can be used. These include commercially available organic halogen compounds with or without synergists.
  • Preferred halogenated, in particular brominated and chlorinated compounds are ethylene-1,2-bistetrabromophthalimide, decabromodiphenylethane, tetrabromobisphenol A epoxyoligomer, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, polypentabromobenzyl acrylate, brominated polystyrene and brominated polyphenylene ethers
  • Preferred synergists are antimony compounds, in particular antimony trioxide and antimony pentoxide, zinc compounds, tin compounds, in particular zinc stannate and borates, in particular zinc borates.
  • the present invention relates to compositions and molding compositions to be produced therefrom and to products containing A) polybutylene terephthalate, B) polyethylene terephthalate, C) aluminum tris (diethylphosphinate), D) Meiern and E) melamine polyphosphate.
  • the present invention also relates to compositions and molding compositions to be prepared therefrom and to products containing A) polybutylene terephthalate, B) polyethylene terephthalate, C) aluminum tris (diethylphosphinate), D) Meiern, E) melamine polyphosphate and F) cyclic phenoxyphosphazene.
  • the present invention additionally relates to compositions and molding compositions to be produced therefrom and to products containing A) polybutylene terephthalate, B) polyethylene terephthalate, C) aluminum tris (diethylphosphinate), D) Meiern, E) melamine polyphosphate and F) cyclic phenoxyphosphazene and G) barium sulfate.
  • the present invention also relates to compositions and molding compositions to be prepared therefrom and to products comprising A) polybutylene terephthalate, B) polyethylene terephthalate, C) aluminum tris (diethylphosphinate), D) Meiern, E) melamine polyphosphate and F) cyclic phenoxyphosphazene, G) barium sulfate and H) glass fibers, preferably glass fibers of E glass, more preferably glass fibers having a mean fiber diameter in the range 10 to 12 ⁇ and / or a mean fiber length of 4.5mm.
  • the present invention also relates to the use of the compositions according to the invention, in particular in the form of molding compositions, for the production of flame-retardant products, preferably electrical or electronic assemblies and components.
  • the present invention also relates to the use of the compositions according to the invention, in particular with high thermal stability against transesterification and high flame resistance according to tests according to UL94 and IEC 60695-2-13, for Production of products of the electrical or electronics industry, in particular products of the electrical or electronics industry in household appliances, wherein at least one further polyalkylene terephthalate and / or a polycycloalkylene terephthalate, in particular at least polybutylene terephthalate is used as polyester in addition to polyethylene terephthalate.
  • the present invention also relates to a process for the production of products, preferably for the electrical or electronics industry, more preferably electronic or electrical assemblies and components, by mixing compositions of the invention into a molding composition.
  • these molding compositions can be discharged in the form of a strand, cooled to granulation and granulated before being subjected as a matrix material to injection molding or extrusion, preferably injection molding.
  • the invention therefore relates to a process for the preparation of products in which compositions according to the invention are mixed into molding compositions, discharged in the form of a strand, cooled to granulation capability and granulated and subjected to injection molding or extrusion as the matrix material.
  • the mixing takes place at temperatures in the range of 240 to 310 ° C, preferably in the range of 260 to 300 ° C, more preferably in the range of 270 to 295 ° C in the melt.
  • a twin-screw extruder is used.
  • the granules containing the composition according to the invention dried, preferably at temperatures in the range of 120 ° C in a vacuum oven or in a dry air dryer for a period of time in the range of 2h before it as a matrix material injection molding or extrusion process for the preparation of inventive products is subjected.
  • the present invention also relates to a method for improving the tracking resistance of polyester-based products by processing compositions of the invention in the form of molding compositions as a matrix material by injection molding or extrusion.
  • Processes according to the invention for producing polyester-based products by extrusion or injection molding operate at melt temperatures in the range from 240 to 330 ° C., preferably in the range from 260 to 300 ° C., more preferably in the range from 270 to 290 ° C. and optionally additionally at pressures of a maximum of 2500 bar, preferably at pressures of at most 2000 bar, more preferably at pressures of at most 1500 bar and most preferably at pressures of at most 750 bar.
  • An injection molding machine consists of a clamping unit, the injection unit, the drive and the controller.
  • the clamping unit includes fixed and movable clamping plates for the tool, a face plate as well as columns and drive of the moving tool clamping plate (toggle joint or hydraulic clamping unit).
  • An injection unit comprises the electrically heatable cylinder, the drive of the worm (motor, gearbox) and the hydraulic system for moving the worm and injection unit.
  • the task of the injection unit is to melt the powder or the granules, to dose, to inject and to press (because of contraction).
  • the problem of backflow of the melt inside the screw (leakage flow) is solved by backflow stops.
  • the inflowing melt is dissolved, cooled and thus manufactured the product to be manufactured. Necessary are always two tool halves.
  • the following functional complexes are distinguished:
  • an endlessly shaped plastic material strand of a molding composition according to the invention is used in the extruder during the extrusion, the extruder being a machine for producing thermoplastic molded pieces.
  • the extruder being a machine for producing thermoplastic molded pieces.
  • references is made here to http://de.wikipedia.org/wiki/Extrusionsblasformen.
  • a distinction is made between single-screw extruders and twin-screw extruders and the respective subgroups of conventional single-screw extruders, conveying-effective single-screw extruders, counter-rotating twin-screw extruders and co-rotating twin-screw extruders.
  • Extrusion plants consist of extruders, tools, downstream equipment, extrusion blow molding.
  • Extrusion lines for the production of profiles consist of: extruder, profile tool, calibration, cooling section, caterpillar and roller take-off, separating device and tilting channel. Consequently, the present invention also relates to products, in particular anti-tracking products, obtainable by extrusion, preferably profile extrusion, or injection molding of the molding compositions obtainable from the compositions according to the invention. Examples
  • the glow wire resistance was determined by means of the glow wire ignition test GWIT (Glow Wire Ignition Temperature) according to DIN EN 60695-2-13.
  • the GWIT test specifies the glow wire ignition temperature, which is 25K (or 30K at temperatures in the range of 900 ° C to 960 ° C) higher than the maximum filament temperature, which in 3 consecutive tests even during the contact time of the filament does not leads to inflammation.
  • Ignition is a flame with a burning time> 5sec. For the tests round plates with a diameter of 80mm and a thickness of 0.75mm were used.
  • the firing time of the flame is also indicated at a filament temperature of 800 ° C.
  • a burning time of 0 seconds means that the sample has not ignited, d. H. also showed no flame with a burning time greater than 0 seconds and less than 5 seconds.
  • Heating "] then cooled again from 280 ° C to 0 ° C at -1 OK / min and finally heated again from + 20K / min from 0 ° C to 280 ° C," 2nd heating "].
  • the shift of the melting peaks between 1. Heating and 2nd heating are considered as a measure of the transesterification and thus as a measure of the thermal stability of the sample.
  • Component C) aluminum tris (diethylphosphinate), (Exolit OP1230 ® from Clariant SE, Muttenz, Switzerland)
  • Component D [CAS No. 225789-38-8.]. [. CAS No. 1502-47-2] Meiern with a melamine content ⁇ 1% (Delacal NFR from Delamin Ltd., Derby, UK)
  • Component E melamine polyphosphate [CAS No. 218768-84-4 (Melapur® 200/70 from BASF, Ludwigshafen, Germany)
  • Phenoxyphosphazenes (Rabitle® FP1 10 [CAS No. 1203646-63-2] from Fushimi Pharmaceutical Co. Ltd, Kagawa
  • Component G barium sulfate [CAS No. 7277-43-7] (BLANC FIXE Super F from Sachtleben Chemie GmbH, Duisburg, Germany)
  • Component H Glass fibers with a diameter of 10 ⁇ m (CS 7967, commercial product of Lanxess NV, Antwerp, Belgium), sized with silane-containing compounds
  • component K the following components, which are customary for use in flameproofed thermoplastic polyesters, were used in the examples as component K / 1):
  • PTS pentaerythritol tetrastearate
  • Thermostabilizer tetrakis (2,4-di-tert-butylphenyl) -1, 1-biphenyl-4,4'-diylbisphosphonite [CAS No. 38613-77-3] (Hostanox® P-EPQ from Clariant International Ltd ., Muttenz, Switzerland)
  • Antidripping additive polytetrafluoroethylene, [CAS No. 9002-84-0] (Dyneon® PA 5932 from Dyneon GmbH & Co. KG, Neuss, Germany)
  • component K / 1 The other additives used (component K / 1)) are the same for corresponding comparative examples and examples in each case in type and amount.
  • Examples 1 and 2 show that a GWIT of at least 825 ° C. with simultaneously high thermal stability with respect to transesterification can be achieved only when using a combination according to the invention comprising component D) and component E). If at least one of the two components D) and / or E) is missing, increased interesterification of the components A) and B) is obtained with one another (compare 1 and compare 2) and / or increased flammability in the glow wire test according to IEC60695-2-13 ( Compare 2 and Cf. 3). For better comparability of Glühdrahtentzündige the sum of the proportions of components C), D), E) and F) in Ex. 1 and Cf. 1 and Ex. 2, Vgl.2 and Vgl. 3 was kept constant in each case.

Abstract

L'invention concerne des compositions, ainsi que des matières à mouler thermoplastiques destinées à être fabriquées à partir de ces compositions et des produits à base de ces matières, contenant outre du polyéthylène téréphtalate au moins un autre polyester choisi dans le groupe des polyalkylène théréphtalates ou des polycycloalkylène théréphtalates, ainsi qu'au moins un sel organique de l'acide phosphinique et/ou au moins un sel organique de l'acide diphosphinique, du mélem et du polyphosphate de mélamine.
PCT/EP2017/069107 2016-09-01 2017-07-28 Matières à mouler thermoplastiques WO2018041492A1 (fr)

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EP17752316.4A EP3507330B1 (fr) 2016-09-01 2017-07-28 Materiaux de moulage thermoplastiques
CN201780053291.2A CN109642071B (zh) 2016-09-01 2017-07-28 热塑性模制混配物
JP2019511864A JP6883093B2 (ja) 2016-09-01 2017-07-28 熱可塑性プラスチック成形コンパウンド物
ES17752316T ES2788711T3 (es) 2016-09-01 2017-07-28 Masas de moldeo termoplásticas
KR1020197005668A KR102341559B1 (ko) 2016-09-01 2017-07-28 열가소성 성형 컴파운드
US16/329,876 US20190241736A1 (en) 2016-09-01 2017-07-28 Thermoplastic molding compounds

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